Living polymerization such as controlled radical polymerization is of interest in polymer chemistry for the preparation of polymers with specific architectures and functionalities leading to the development of materials with tailored properties. Controlled radical polymerization, particularly Atom Transfer Radical Polymerization, has been conducted to prepare so-called “polymer brushes” on the surfaces of various substrates in which the polymer chains are tethered to the substrate surface. For example, an ATRP initiator is first attached to the substrate surface and polymer chains are then grafted from the substrate surface to form a coating layer. These coatings can be of molecular dimensions when the molecule used for attaching the initiator to the substrate surface is a SAM. For certain substrates such as glass and plastics, the SAM containing initiator for controlled radical polymerization does not adhere well to the substrate surface. This often results in failure of the coating layer.